33394-10-4

Upstream product

• 94070-38-9 trans-MeOIr(CO)(PPh₃)2 
• 203629-39-4 (P(C₆H₅)3)2(CO)Ir(NC₄H₄)(C(O)CH₃)Cl 
• 94070-40-3 trans-PhOIr(CO)(PPh₃)2 

Downstream Products

• 17000-10-1 HIrCl₂(CO)(PPh₃)2 

Relevant academic research and scientific papers

Oxidative addition and reductive elimination reactions of trans-[Ir(PPh3)2(CO)(NC4H4)] and trans,cis-[Ir(PPh3)2(H)2(CO)(NC 4H4)], including N-H bond-forming reductive elimination of pyrrole

The complex trans-(PPh3)2(CO)Ir(NC4H4) (1) has been synthesized and is an analogue of metal-aryl complexes, but with a nitrogen of the heteroaromatic group covalently bonded to the transition metal. Compound 1 readily undergoes initial reaction with a variety of substrates at the metal center rather than at the pyrrolyl nitrogen, allowing for the study of reactions between the pyrrolyl group and accompanying covalent ligands. These reactions ultimately produce N-substituted pyrroles, X-NC4H4 (X = C(O)CH3, C(O)C6H4CH3, H, SnMe3, SiMe3, SiEt3, Bcat). Compound 1 undergoes oxidative addition of H2 to form the stable Ir-(III) product (PPh3)2(CO)Ir(H)2(NC4H4) (2). When pure 2 is heated, it undergoes simple elimination of H2 to regenerate 1; however, if 2 is heated for longer times under H2 in the presence of PPh3, it undergoes reductive elimination of pyrrole and forms (PPh3)3(CO)Ir(H). Qualitative analysis of the mechanism of this reaction suggests that it occurs by either direct reductive elimination from the octahedral complex or rate-determining ligand dissociation, followed by rapid reductive elimination of pyrrole. Reductive elimination of pyrrole from 2 was also observed to occur photochemically by initial irreversible dissociation of a dative ligand.

Reactions of iridium(I) alkoxide complexes with acyl and alkyl sources: Carbon-oxygen bond-forming reactions

The reactions of alkoxyiridium complexes trans-ROIr(CO)(PPh3)2 (R = Me, Ph, t-Bu, i-Pr) with organic substrates R′X (R′ = Me, CH3C(O), C6H5C(O), C6H5CH2C(O), HC(O); X = Cl, I, H)

Selectivity in C-O bond formation: Reaction of acid chlorides and methyl iodide with trans-MeOIr(CO)(PPh3)2

Reactions of RX (RX = MeI, CH3C(O)Cl, C6H5C(O)Cl, and C6H5CH2C(O)Cl) with trans-MeOIr(CO)(PPh3)2 have been examined. In each case, an adduct is formed, RIr(OMe)(CO)(PPh3)2X, which is stable for R = Me. For the acid chlorides, this adduct eliminates ester, forming Ir(CO)(PPh3)2Cl. Thus the carbon-oxygen bond leading to ester products is formed more readily than the carbon-oxygen bond leading to dimethyl ether.

NEW COORDINATIVELY UNSATURATED ACYLIRIDIUM(III) COMPOUNDS INCLUDING A NEW PYRUVOYL COMPLEX. SYNTHESIS, KINETICS AND THERMOCHEMISTRY

The reaction of acyl chlorides with trans- have been used to prepare new examples of coordinatively unsaturated acyliridium(III) complexes, (PPh3)2> (R = CH2Cl, CH2OPh, C(O)OEt, CH2CH2C(O)OMe or C(O)CH3).In the case of ethyl malonyl chloride a chelated complex is obtained: .All of these complexes undergo a spontaneous migration reaction to give the coordinatively saturated product .The coordinatively unsaturated pyruvoyl complex behaves atypically.Exposure of the solid to light yields the acetyl complex, (CO)(PPh3)2>, while heating the solid in the dark yields the methyl complex, .A coordinatively saturated pyruvoyl complex is obtained by addition of pyruvoyl chloride to Vaska's complex.The rates of migration of CH2Cl, CH2OPh and C(O)OEt were determined in ethylene dichloride solution and the ground state enthalpy change for the migration of these groups was obtained by differential scanning calorimetry as was that for conversion of (PPh3)2> to + CO.